# Patent

## Title
Polyethylene films having high resistance to deformation or elongation

## Abstract

Disclosed is a method for producing polyethylene films which have high resistance to deformation or elongation under loading in tension. The method comprises orienting in the machine direction (MD) a high density polyethylene film at a draw-down ratio effective to give the film an MD tensile strength at yield greater than or equal to 50,000 psi, wherein the HDPE has a density greater than 0.940 g/cm3.

## Background
FIELD OF THE INVENTION
The invention relates to polyethylene films. More particularly, the invention relates to polyethylene films which have high resistance to deformation or elongation under loading in tension.
BACKGROUND OF THE INVENTION
Polyethylene is divided into high-density (HDPE, density 0.941 g/cm3 or greater), medium-density (MDPE, density from 0.926 to 0.940 g/cm3), low-density (LDPE, density from 0.910 to 0.925 g/cm3), and linear low-density polyethylene (LLDPE, density from 0.910 to 0.925 g/cm3). See ASTM D4976-98: Standard Specification for Polyethylene Plastic Molding and Extrusion Materials. Polyethylene can also be divided by molecular weight. For instance, ultra-high molecular weight polyethylene denotes those which have a weight average molecular weight (Mw) greater than 3,000,000. See U.S. Pat. No. 6,265,504. High molecular weight polyethylene usually includes those which have an Mw from 130,000 to 1,000,000.
One of the main uses of polyethylene (HDPE, LLDPE, and LDPE) is in film applications, such as grocery sacks, institutional and consumer can liners, merchandise bags, shipping sacks, food packaging films, multi-wall bag liners, produce bags, deli wraps, stretch wraps, and shrink wraps. The key physical properties of polyethylene film include tear strength, impact strength, tensile properties, stiffness and transparency. Tensile properties are an important indicator of the material's behavior under loading in tension. Tensile properties include tensile strength at yield, tensile strength at break (ultimate tensile strength), tensile modulus (Young's modulus), and elongation at yield and break. High tensile strength at yield is required for heavy duty bags such as those for trash, top soil, and fertilizer. High tensile strength at yield means high resistance to deformation or elongation under loading.
Machine direction orientation (MDO) is known to the polyolefin industry. When a polymer is strained under uniaxial stress, the orientation becomes aligned in the direction of pull. For instance, U.S. Pat. No. 6,391,411 teaches the MDO of very high molecular weight (both Mn and Mw greater than 1,000,000) HDPE films. However, MDO of very high molecular weight HDPE films are limited because these films are difficult to stretch to a high draw-down ratio.
Polyethylene films, although having many desirable properties for the use in heavy duty bags, have low tensile strength at yield. Imagine that a person carries a 50-pound trash bag, while the bag elongates to five-foot long. She or he will feel unsafe and inconvenient. It would be desirable to prepare a polyethylene film which, along with other properties, has high tensile strength at yield so that the film can be used for heavy duty bags.
SUMMARY OF THE INVENTION
The invention is a method for preparing a polyethylene film which has high resistance to deformation or elongation under load in tension. The method comprises orienting in the machine direction (MD) a high density polyethylene (HDPE) film at a draw-down ratio effective to give the film an MD tensile strength at yield greater than or equal to 50,000 psi. The HDPE has a density greater than 0.940 g/cm3. Preferably, the HDPE has a density within the range of 0.950 to 0.965 g/cm3, a weight average molecular weight (Mw) within the range of 130,000 to 1,000,000, and a number average molecular weight (Mn) within the range of 10,000 to 500,000.


DETAILED DESCRIPTION OF THE INVENTION
Tensile properties are an important indicator of the material's behavior under loading in tension. Tensile properties include tensile strength at yield, tensile strength at break (ultimate tensile strength), tensile modulus (Young's modulus), and elongation at yield and break. Tensile strength at yield is the maximum stress at which permanent, non-elastic deformation begins. Yield point is the point (load) at which the material yields, i.e., increase in strain occurs without an increase in stress. Ultimate tensile strength is the maximum stress a material can withstand before failing. Elongation at yield is the strain that the material undergoes at the yield point, or the percent change in length that occurs while the material is stressed to its yield point. Elongation at break is the strain at failure, or the percent change in length at failure. Tensile, or Young's modulus, is the ratio of stress to strain within the elastic region of the stress-strain curve (prior to the yield point).
The method of the invention provides polyethylene films having improved tensile properties. The method comprises orienting in the machine direction (MD) a high density polyethylene (HDPE) film at a draw-down ratio effective to give the film an MD tensile strength at yield greater than or equal to 50,000 psi. Polyethylene resins suitable for making the HDPE film for the use in the invention have a density greater than 0.940 g/cm3. Preferably the density is within the range of about 0.941 to about 0.965 g/cm3. More preferably, the density is within the range of about 0.949 to about 0.959 g/cm3.
Preferably, the polyethylene resins have a number average molecular weight (Mn) within the range of about 10,000 to about 500,000, more preferably from about 11,000 to about 50,000, and most preferably from about 11,000 to about 20,000. Preferably, the polyethylene resin has a weight average molecular weight (Mw) within the range of about 130,000 to about 1,000,000, more preferably from about 150,000 to about 500,000, and most preferably from about 155,000 to about 250,000. Preferably, the polyethylene resin has a molecular weight distribution (Mw/Mn) within the range of about 5 to about 20, more preferably from about 7 to about 18, and most preferably from about 9 to about 17.
The Mw, Mn and Mw/Mn are obtained by gel permeation chromatography (GPC) on a Waters GPC2000CV high temperature instrument equipped with a mixed bed GPC column (Polymer Labs mixed B-LS) and 1,2,4-trichlorobenzene (TCB) as the mobile phase. The mobile phase is used at a nominal flow rate of 1.0 mL/min and a temperature of 145° C. No antioxidant is added to the mobile phase, but 800 ppm BHT is added to the solvent used for sample dissolution. Polymer samples are heated at 175° C. for two hours with gentle agitation every 30 minutes. Injection volume is 100 microliters.
The Mw and Mn are calculated using the cumulative matching % calibration procedure employed by the Waters Millennium 4.0 software. This involves first generating a calibration curve using narrow polystyrene standards (PSS, products of Waters Corporation), then developing a polyethylene calibration by the Universal Calibration procedure.
Preferably, the polyethylene resins have a melt index MI2 from about 0.03 to about 0.15 dg/min, more preferably from about 0.04 to about 0.15 dg/min, and most preferably from 0.05 to 0.10. The MI2 is measured at 190° C. under 2.16 kg of pressure according to ASTM D-1238. In general, the higher the molecular weights, the lower the MI2 values.
Preferably, the polyethylene resins are copolymers that comprise from about 90 wt % to about 98 wt % of recurring units of ethylene and from about 2 wt % to about 10 wt % of recurring units of a C3 to C10 α-olefin. Suitable C3 to C10 α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and 1-octene, and the like, and mixtures thereof.
Suitable polyethylene resins can be produced by Ziegler catalysts or single-site catalysts. Ziegler catalysts are well known. Examples of suitable Ziegler catalysts include titanium halides, titanium alkoxides, vanadium halides, and mixtures thereof. Ziegler catalysts are used with cocatalysts such as alkyl aluminum compounds.
Single-site catalysts can be divided into metallocene and non-metallocene. Metallocene single-site catalysts are transition metal compounds that contain cyclopentadienyl (Cp) or Cp derivative ligands. For example, U.S. Pat. No. 4,542,199, the teachings of which are incorporated herein by reference, teaches metallocene catalysts. Non-metallocene single-site catalysts contain ligands other than Cp but have the same catalytic characteristics as metallocenes. The non-metallocene single-site catalysts may contain heteroatomic ligands, e.g., boraaryl, pyrrolyl, azaborolinyl or quinolinyl. For example, U.S. Pat. Nos. 6,034,027, 5,539,124, 5,756,611, and 5,637,660, the teachings of which are incorporated herein by reference, teach non-metallocene catalysts.
The polyethylene resins are converted into thick films by a high-stalk or in-pocket blown extrusion process. Both high-stalk and in-pocket processes are commonly used for making polyethylene films. The difference between the high-stalk process and the in-pocket process is that in the high-stalk process, the extruded tube is inflated a distance (i.e., the length of the stalk) from the extrusion die, while the extruded tube in the in-pocket process is inflated as the tube exits the extrusion die.
For instance, U.S. Pat. No. 4,606,879, the teachings of which are herein incorporated by reference, teaches high-stalk blown film extrusion apparatus and method. The process temperature is preferably within the range of about 150° C. to about 210° C. The thickness of the film is preferably within the range of about 3 to about 14 mils, more preferably within the range of about 6 to about 8 mils.
The blown films are then uniaxially stretched in the machine (or processing) direction to a thinner film. The ratio of the film thickness before and after orientation is called “draw-down ratio.” For example, when a 6-mil film is stretched to 0.6-mil, the draw-down ratio is 10:1. The draw-down ratio of the method of the invention is preferably greater than or equal to 7:1. More preferably, the draw-down ratio is greater than or equal to 10:1. Most preferably, the draw-down ratio is greater than or equal to 11:1.
During the MDO, the film from the blown-film line is heated to an orientation temperature. Preferably, the orientation temperature is between 60% of the difference between the glass transition temperature (Tg) and the melting point (Tm) and the melting temperature (Tm). For instance, if the blend has a Tg of 25° C. and a Tm of 125° C., the orientation temperature is preferably within the range of about 60° C. to about 125° C. The heating is preferably performed utilizing multiple heating rollers.
Next, the heated film is fed into a slow draw roll with a nip roller, which has the same rolling speed as the heating rollers. The film then enters a fast draw roll. The fast draw roll has a speed that is 2 to 10 times faster than the slow draw roll, which effectively stretches the film on a continuous basis.
The stretched film then enters annealing thermal rollers, which allow stress relaxation by holding the film at an elevated temperature for a period of time. The annealing temperature is preferably within the range of about 100° C. to about 125° C. and the annealing time is within the range of about 1 to about 2 seconds. Finally, the film is cooled through cooling rollers to an ambient temperature.
The invention includes the MD oriented (MDO) film made by the method. The MDO film has an MD tensile strength at yield greater than or equal to 50,000 psi. Tensile strength is tested according to ASTM D-882. Preferably, the MDO film has an MD tensile strength at yield greater than about 55,000 psi. Most preferably, the MDO film has an MD tensile strength at yield greater than about 69,000 psi.
Preferably, the MDO film has an MD Young's modulus greater than or equal to 500,000 psi. More preferably, the MD Young's modulus is greater than 900,000 psi. Most preferably, the MD Young's modulus is greater than 1,000,000 psi. Preferably, the MDO film has an MD tensile strength at break greater than 40,000 psi. More preferably, the MD tensile strength at break is greater than 50,000 psi. Most preferably, the MD tensile strength at break is greater than 55,000 psi.
Preferably, the MDO film has an MD elongation at yield is less than 25%. More preferably, the MD elongation at yield is less than 20%. Most preferably, the MD elongation at yield is less than 15%. Preferably, the MDO film has an MD elongation at break less than 50%. More preferably, the MD elongation at break is less than 25%. Most preferably, the MD elongation at break is less than 14%. Preferably, the MDO film has an MD elongation at yield which is essentially the same as the MD elongation at break.
The MDO film preferably remains at high transverse direction (TD) properties. Preferably, the MDO film has a TD Young's modulus greater than 300,000 psi; more preferably, greater than 350,000 psi. Preferably, the MDO film has a TD elongation at yield less than 4%, more preferably less than 3.5%. Preferably, the MDO film has a TD tensile strength at yield greater than 5,000 psi. Preferably, the MDO film has a TD elongation at break less than 400%, more preferably less than 300%. Preferably, the MDO film has a TD tensile strength at break greater than 3,500 psi.
The following examples merely illustrate the invention. Those skilled in the art will recognize many variations that are within the spirit of the invention and scope of the claims.
EXAMPLES 1-11
Machine Direction Orientation of High Density (0.959 g/cm3) High Stalk Polyethylene Films
A high density polyethylene (L5906, product of Equistar Chemicals, LP, MI2: 0.057 dg/min, density: 0.959 g/cm3, Mn: 12,900, Mw: 207,000, and Mw/Mn: 16) is converted into films with a thickness of 6.0 mil on 200 mm die with 2 mm die gap. The films are produced at a stalk height of 8 die diameters and at blow-up ratios (BUR) of 4:1.
The films are then stretched into thinner films in the machine direction with draw-down ratios 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and 11.6 in Examples 1-11, respectively. When the draw-down ratio is 1:1, the film is not oriented. The draw-down ratio of 11.6:1 is the maximum draw-down ratio limited by the orientation equipment and not the polymer film. The film properties are listed in Table 1. The data shows that as the films are oriented in the machine direction, the percent change in the difference between the MD break elongation % and MD yield elongation % relative to the unoriented film decreases to the point where the MD break elongation % is nearly identical to the MD yield elongation %. Similarly, as the draw-down ratio increases, the MD yield and break strengths substantially increase, indicating the film can withstand a significantly heavier load prior to both yielding (stretching) and breaking. A similar convergence in yield and break elongation %, but to a lesser degree, is seen in the transverse-direction properties of the films.
EXAMPLES 12-22
Machine Direction Orientation of High Density (0.959 g/cm3) In-pocket Polyethylene Films
Examples 1-11 are repeated, but the films are made at in-pocket film line. The film properties are listed in Table 2, which shows that the machine direction oriented, in-pocket films have similar MD and TD tensile properties as the high stalk films at the various draw ratios. The draw-down ratio of 11.3:1 is the maximum draw-down ratio limited by the orientation equipment and not the polymer film. The enhancements in tensile properties for examples 12-22 are similar to those discussed for examples 1-11.
EXAMPLES 23-30
Machine Direction Orientation of High density Films of Various Densities and MI2 
Three Equistar high density polyethylene resins, XL3805 (density: 0.940 g/cm3, MI2: 0.057 dg/min, Mn: 18,000, Mw: 209,000), XL3810 (density: 0.940 g/cm3, MI2: 0.12 dg/min, Mn: 16,000, Mw: 175,000), L4907 (density: 0.949 g/cm3, MI2: 0.075 dg/min, Mn: 14,300, Mw: 194,700), and L5005 (density: 0.949 g/cm3, MI2: 0.057 dg/min, Mn: 12,600, Mw: 212,000) are converted into films of thickness of 6.0 mil by the high stalk process described in Examples 1-11 and the in-pocket process described in examples 12-22. The blown films are then stretched in the machine direction. Listed in Table 3 are the machine direction and transverse direction tensile properties of each oriented film at their maximum draw-down ratios. The table shows that the tensile property enhancements depend on the density and MI2 of the polyethylene resin, the blown film process, and maximum draw-down ratio of the MDO.







TABLE 1







Properties vs. Draw-down Ratio of High Density (0.959 g/cm3), High Stalk Films










Properties in Machine Direction (MD)
Properties in Transverse Direction (TD)























Elonga-
Tensile

Tensile
Elongation

Elonga-
Tensile

Tensile
Elongation



Draw-

tion
strength
Elongation
strength
@ break/
Modu-
tion
strength
Elongation
strength
@ break/


Ex.
down
Modulus
@ yield
@ yield
@ break
@ break
elongation
lus
@ yield
@ yield
@ break
@ break
elongation


No.
ratio
psi
%
psi
%
psi
@ yield
psi
%
psi
%
psi
@ yield























1
1:1
188,600
8.0
 4,800
470
 5,500
59
196,200
6.0
5,100
690
5,100
115


2
2:1
224,500
17
 7,400
310
10,900
18
248,600
4.7
4,600
680
4,900
145


3
3:1
267,300
20
12,500
200
14,900
10
279,300
4.5
4,800
660
4,700
147


4
4:1
318,200
21
20,500
130
19,300
6
301,000
4.4
5,000
610
4,500
139


5
5:1
378,800
23
30,200
88
25,200
4
317,900
4.2
5,200
550
4,250
131


6
6:1
451,000
25
40,900
58
33,100
2.3
331,700
4.1
5,400
460
4,000
112


7
7:1
537,000
22
51,000
38
42,700
1.7
343,300
3.8
5,600
380
3,800
100


8
8:1
639,200
20
58,500
25
52,600
1.3
353,400
3.6
5,800
300
3,700
83


9
9:1
761,000
16
69,000
16
61,200
1
362,300
3.6
5,700
240
3,600
67


10
10:1 
906,000
15
69,700
15
65,600
1
370,200
3.4
5,400
210
3,700
62


11
11:1 
1,197,600  
14
70,400
14
55,300
1
381,500
3.3
5,100
230
3,900
70
















TABLE 2







Properties vs. Draw-down Ratio of High Density (0.959 g/cm3), In-pocket Films









Properties in Transverse Direction (TD)












Properties in Machine Direction (MD)

Tensile
























Elonga-
Tensile

Tensile
Elongation

Elonga-
Tensile

strength
Elongation



Draw-

tion
strength
Elongation
strength
@ break/
Modu-
tion
strength
Elongation
@
@ break/


Ex.
down
Modulus
@ yield
@ yield
@ break
@ break
elongation
lus
@ yield
@ yield
@ break
break,
elongation


No.
ratio
psi
%
psi
%
psi
@ yield
psi
%
psi
%
psi
@ yield























12
1:1
189,000
7.0
 4,700
640
 6,200
91
222,800
6.0
5,300
750
5,300
125


13
2:1
225,100
13
 6,700
290
11,100
22
262,600
3.9
4,500
600
5,100
154


14
3:1
268,200
30
15,900
120
16,100
4.0
285,900
3.7
4,600
630
4,900
170


15
4:1
319,500
41
24,500
53
21,100
1.3
302,400
3.6
4,700
660
4,600
183


16
5:1
380,700
36
29,900
39
26,100
1.1
315,300
3.8
4,800
610
4,400
161


17
6:1
453,600
31
36,800
40
31,100
1.3
325,700
4.2
4,900
530
4,200
126


18
7:1
540,300
27
43,200
38
36,100
1.4
334,600
4.5
5,000
470
3,900
104


19
8:1
643,700
18
50,200
29
41,000
1.6
342,300
4.6
5,400
570
3,700
124


20
9:1
767,000
15
54,000
28
46,000
1.9
349,000
4.3
5,200
610
3,500
142


21
10:1 
913,700
13
61,000
19
51,000
1.5
355,100
4.5
5,100
550
3,200
122


22
11.3:1  
1,147,300  
12
65,100
19
57,500
1.6
362,100
4.7
4,600
500
2,900
106
















TABLE 3







Properties vs. Draw-down Ratio of High density Films of Various Densities and MI2









Properties in Machine Direction (MD)












MDO

Tensile

















Resin

Max.

Tensile

strength
Elongation



Properties

Draw-

strength
Elongation
@
@ break/
















Ex.
Density
MI2
Film
Down
Elongation
@ yield,
@ break,
break,
Elongation


No.
g/cm3
dg/min
Process
Ratio
@ yield, %
psi
%
psi
@ yield



















11
0.959
0.057
High Stalk
11.6:1
14
70,400
14
55,200
1


22
0.959
0.057
In-pocket
11.3:1
12
65,100
19
57,500
1.6


23
0.940
0.057
High Stalk
 8.3:1
3
 8,400
30
52,200
10


24
0.940
0.057
In-pocket
 7.6:1
2
 7,600
28
53,600
14


25
0.940
0.12
High Stalk
 6.5:1
3
 7,200
41
32,900
14


26
0.940
0.12
In-pocket
 2.2:1
16
 4,800
320
11,400
20


27
0.949
0.075
High Stalk
11.9:1
12
56,600
12
55,500
1


28
0.949
0.075
In-pocket
 7.7:1
2
 9,200
25
52,700
13


29
0.949
0.057
High Stalk
10.6:1
3
13,600
19
53,200
6


30
0.949
0.057
In-pocket
10.0:1
10
51,200
29
63,500
3












Properties Transverse Direction (TD)












Tensile

Tensile
Elongation



strength

strength
@ break/














Ex.
Elongation
@ yield,
Elongation
@ break,
elongation



No.
@ yield, %
psi
@ break, %
psi
@ yield


















11
3.3
5,100
230
3,900
70



22
4.7
4,600
500
2,900
106



23
4
4,700
710
4,900
178



24
4
4,500
740
4,400
185



25
4
4,500
730
4,300
183



26
6
3,700
770
4,800
128



27
2.9
4,000
470
3,500
162



28
4
4,900
710
4,000
178



29
4
4,800
690
3,500
173



30
4
5,300
700
4,100
175

## Claims

1. A method comprising the steps of:
receiving a high stalk, high density polyethylene (HDPE) film from a blown-film line
orienting in the machine direction the high stalk, high density polyethylene (HDPE) film wherein the orienting step further comprises the steps of:
heating the high stalk, high density polyethylene film using a plurality of heating rollers to an orientation temperature to produce a heated film, wherein the orientation temperature is between (i) 60% of the difference between the glass transition temperature and the melting temperature; and, (ii) the melting temperature;
feeding the heated film into a plurality of rollers wherein the plurality of rollers stretches the film on a continuous basis to produce a stretched film;
annealing the stretched film to produce an annealed film; and,
cooling the annealed film wherein the cooled film has a
machine direction tensile strength at yield greater than 69,000 psi and a draw-down ratio greater than or equal to 11:1, wherein
the HDPE has a density greater than 0.940 g/cm3,
the HDPE has a weight average molecular weight (Mw) within the range of 150,000 to 500,000,
the HDPE has a number average molecular weight (Mn) within the range of 11,000 to 20,000, and
the HDPE has a molecular weight distribution (Mw/Mn) within the range of 9 to 20.

2. The method of claim 1 wherein the HDPE has a density greater than or equal to 0.949 g/cm3.

3. The method of claim 1 wherein the HDPE has a density within the range of 0.949 g/cm3 to 0.965 g/cm3.

4. The method of claim 1 wherein the HDPE has a density within the range of 0.949 g/cm3 to 0.959 g/cm3.

5. The method of claim 1 wherein the Mw is within the range of 155,000 to 300,000.

6. The method of claim 1 wherein the Mw is within the range of 155,000 to 250,000.

7. The method of claim 1 wherein the oriented film has an elongation at break that is essentially the same as its elongation at yield.

8. The method of claim 1 wherein the molecular weight distribution is within the range of from 9 to 17.

9. The method of claim 1 wherein the HDPE has a melt index MI2 of from about 0.02 to about 0.15 dg/min.

10. The method of claim 9 wherein the melt index MI2 is from about 0.04 to about 0.15 dg/min.

11. The method of claim 9 wherein the melt index MI2 is from about 0.05 to about 0.10 dg/min.

12. The method of claim 1 wherein the HDPE is a copolymer comprising from about 90 wt % to about 98 wt % recurring units of ethylene and from 2 wt % to about 10 wt % of recurring units of a C3-C10 α-olefin.

13. The method of claim 12 wherein the C3-C10 α-olefin is selected from the group of propylene, 1-butene, 1-pentene, 1-bexene, 4-methyl-1-pentene, 1-octene, and mixtures thereof.